CN117820599B - Preparation method of ultraviolet light curing softening and cracking preventing agent, positive electrode slurry and preparation method thereof, and preparation method of positive electrode plate - Google Patents
Preparation method of ultraviolet light curing softening and cracking preventing agent, positive electrode slurry and preparation method thereof, and preparation method of positive electrode plate Download PDFInfo
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- CN117820599B CN117820599B CN202410238751.0A CN202410238751A CN117820599B CN 117820599 B CN117820599 B CN 117820599B CN 202410238751 A CN202410238751 A CN 202410238751A CN 117820599 B CN117820599 B CN 117820599B
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- positive electrode
- ultraviolet light
- diisocyanate
- electrode slurry
- light curing
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 98
- 238000005336 cracking Methods 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 81
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 29
- 239000010452 phosphate Substances 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- -1 acrylic ester Chemical class 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 71
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 34
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 125000005442 diisocyanate group Chemical group 0.000 claims description 24
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 20
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 20
- 239000011343 solid material Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 17
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 16
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 16
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- 150000005690 diesters Chemical class 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 10
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000003944 tolyl group Chemical group 0.000 claims description 8
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 7
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 7
- HDFFVHSMHLDSLO-UHFFFAOYSA-M dibenzyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)([O-])OCC1=CC=CC=C1 HDFFVHSMHLDSLO-UHFFFAOYSA-M 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 6
- 239000006256 anode slurry Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000004713 phosphodiesters Chemical class 0.000 claims description 4
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- GPKUICFDWYEPTK-UHFFFAOYSA-N methoxycyclohexatriene Chemical group COC1=CC=C=C[CH]1 GPKUICFDWYEPTK-UHFFFAOYSA-N 0.000 claims description 3
- RIOOIQBUNJDFON-UHFFFAOYSA-N methyl 2-methylprop-2-enoate oxolane Chemical compound O1CCCC1.COC(C(=C)C)=O RIOOIQBUNJDFON-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002003 electrode paste Substances 0.000 claims 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 13
- 239000002002 slurry Substances 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008719 thickening Effects 0.000 abstract description 2
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 13
- 239000012965 benzophenone Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005056 compaction Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 101000588031 Heliothis armigera entomopoxvirus Spindolin Proteins 0.000 description 3
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- 238000010998 test method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a preparation method of an ultraviolet light curing flexibility-increasing cracking-preventing agent, which comprises three steps of synthesis of phosphoric triol, synthesis of trifunctional phosphate modified polyurethane acrylic ester and synthesis of the ultraviolet light curing flexibility-increasing cracking-preventing agent, as well as positive electrode slurry and a preparation method thereof, and a preparation method of a positive electrode plate. The ultraviolet light curing flexibility-increasing cracking-preventing agent disclosed by the invention not only can obviously improve the cracking degree of the positive electrode plate slurry, increase the flexibility and the stripping force of the positive electrode plate, but also can further improve the viscosity and the stability of the positive electrode plate slurry, is simple in manufacturing process, can realize the functions of thickening and preventing cracking of the positive electrode plate without complex process conditions such as two-layer coating and the like, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of an ultraviolet light curing softening and cracking preventing agent, positive electrode slurry and a preparation method thereof, and a preparation method of a positive electrode plate.
Background
With the vigorous development of the new energy automobile industry, the new energy automobile market continuously puts higher demands on the energy density, the cycle life, the battery cost and the safety performance of the lithium ion power battery. Therefore, battery manufacturers pay high attention to quality control in the production process of lithium ion batteries, strive to improve the quality and consistency of products and reduce the production cost as much as possible.
The manufacturing of the pole piece occupies an important position in the whole lithium ion battery process development, the quality of the pole piece not only affects the middle section assembly process of the battery, but also can have critical influence on the later section process, the electrochemical performance and the safety performance of the battery, and researches show that the pole piece manufacturing technology can greatly reduce the manufacturing cost of the battery. Various coating and drying defects may occur in the actual pole piece coating and drying process, which is unfavorable for preparing pole pieces with uniform thickness and surface density, and seriously affects the performance and yield of the pole pieces. Defects that may occur during the pole piece coating and drying process are largely classified into three categories: point defects, line defects, and edge defects. The main causes of these defects are: the slurry has poor flexibility and large stress; agglomerate particles exist on the surface of the pole piece; contamination by objects of lower surface tension (e.g., oil droplets, dust, etc.) during coating; bubbles in the wet film migrate from the inner layer to the surface and collapse at the film surface; the slurry viscosity is too low or the solids content is too low; the surface density of the polar plate is uneven; the slurry does not match the surface tension of the substrate, etc. Thus, potential safety hazards of piercing the diaphragm and short circuit can be caused, and adverse effects are caused on the voltage, voltage attenuation, cycle life and the like of the battery. The agglomerate particles, bubbles, pollutants, viscosity and solid content can be solved by the existing means such as a dispersing agent, a deaerator and the like, the coating thickness can be reduced, the flexibility can be improved, but the energy density of a pole piece is greatly influenced, but the problem of poor flexibility of slurry itself is not solved well, for example, patent CN 116493219A discloses an atomization system for preventing the pole piece from cracking, but the disadvantage is that the cost is higher on one hand, the humidity of the working environment is higher on the other hand, the current positive electrode slurry solvent is mainly N-methyl pyrrolidone (NMP), otherwise, the cracking problem is more serious, the slurry and NMP which is not volatilized in the pole piece in the drying process easily absorb moisture in the air to reduce the solubility of PVDF, and thus the slurry gel is jelly-like to influence the processing performance.
Therefore, it is necessary to develop an ultraviolet curing softening and cracking preventing agent to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of an ultraviolet light curing flexibility-increasing cracking-preventing agent, positive electrode slurry and a preparation method thereof, and a preparation method of a positive electrode plate.
The technical scheme of the invention is as follows:
a preparation method of an ultraviolet light curing softening and cracking preventing agent comprises the following steps:
Step one, synthesizing phosphoric triol: adding glycidyl ether into a first reaction bottle, stirring and heating to 70 ℃, then slowly adding phosphoric diester into the first reaction bottle within 1h, continuously stirring, keeping the temperature at 70 ℃, heating to 90-100 ℃ after the phosphoric diester is added, and reacting for 3h until the pH value of a reactant is lower than 10 and the epoxy value is lower than 0.01, thus obtaining a product phosphoric triol;
Step two, synthesizing trifunctional phosphate modified polyurethane acrylic ester: adding diisocyanate into a second reaction bottle, stirring and heating to 40-50 ℃, adding hydroquinone and dibutyltin dilaurate into the second reaction bottle, slowly adding hydroxyl acrylate into the second reaction bottle, keeping the temperature at 40-50 ℃, when the isocyanate content in reactants is constant, obtaining a semi-adduct, quickly adding phosphoric triol and reactive diluent into the second reaction bottle, simultaneously raising and keeping the temperature at 70 ℃, reacting until no NCO characteristic peak is detected by infrared, and obtaining the trifunctional phosphate modified polyurethane acrylate, wherein the molar ratio of dibutyltin dilaurate to the diisocyanate is 0.5: 100-1: 100; the molar ratio of hydroquinone to diisocyanate was 0.1:100 to 0.2:100; the molar ratio of the hydroxy acrylate to the diisocyanate was 0.95:1 to 1:1, a step of; the molar ratio of the phosphoric triol to the diisocyanate was 0.33:1 to 0.35:1, a step of; the molar ratio of reactive diluent to diisocyanate was 0.25:1 to 0.5:1, a step of;
Step three, synthesizing an ultraviolet light curing softening and cracking preventing agent: adding a photoinitiator into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the addition amount of the photoinitiator accounts for 2% -10% of the total weight of the ultraviolet light curing flexibilizer anti-cracking agent.
Further, the reaction formula of the first step is:
，
Wherein,
A is a phosphodiester;
b is glycidyl ether;
p is a phosphoric triol;
r is any one of n-butyl, methyl, phenyl and tolyl;
the structural formula of R 1 is as follows:
。
Further, in step one, the molar ratio of the phosphodiester to the glycidyl ether is 3:1.
The abbreviation structural formula of the phosphoric triol is as follows:
，
The reaction formula of the second step is:
，
Wherein,
C is a diisocyanate;
d is hydroxy acrylate;
e is a semi-adduct;
p is a phosphoric triol;
f is trifunctional phosphate modified urethane acrylate;
r 2 is any one of tolyl, hexamethylene, isophorone, m-xylylene and benzhydryl;
r 3 is any one of ethyl and propyl.
Further, the phosphoric diester is any one of dibutyl phosphate, dimethyl phosphate, dibenzyl phosphate and diphenyl phosphate; the diisocyanate is any one of toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate and diphenylmethane diisocyanate; the hydroxyl acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the reactive diluent is any one or a combination of a plurality of glycidyl methacrylate, isopropyl methacrylate, tetrahydrofuran methyl methacrylate, styrene, vinyl acetate, N-vinyl pyrrolidone, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate; the photoinitiator is any one or a combination of a plurality of diphenyl ketone, P- (2-ethylamino) diphenyl ketone, 2- (P-methoxyphenyl) -4, 5-diphenyl-tut-tut-diphenyl-m-ethyl ketone, 2-dichloro-4-phenoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone and methyl benzoate.
The other technical scheme of the invention is as follows:
an ultraviolet light curing flexibilizing and cracking-preventing agent positive electrode slurry, comprising: a solid material and an organic solvent, the weight of the organic solvent accounting for 40wt% of the total weight of the positive electrode slurry, the solid material accounting for 100wt% of the total weight, comprising: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binder, 2.5wt% of conductive agent and 95.4wt% of lithium iron phosphate, wherein the binder is any one or a combination of more of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and polyacrylic acid; the conductive agent is any one or a combination of a plurality of KS-6, KS-15, SFG-6, SFG-15, acetylene black, super P, super S, 350G, carbon fiber, carbon nano tube and active carbon; the organic solvent is any one or a combination of more of N-methyl pyrrolidone, ethyl acetate, methyl propionate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
And further, mixing an organic solvent, an ultraviolet light curing softening and cracking preventing agent, a binder and a conductive agent, and finally adding lithium iron phosphate and uniformly mixing to obtain the anode slurry.
The third technical scheme of the invention is as follows:
the preparation method of the positive electrode plate of the positive electrode slurry comprises the steps of taking aluminum foil as a base material, coating the positive electrode slurry on the base material, wherein the coating thickness of the positive electrode slurry is 350 mu m, then placing the positive electrode slurry in an oven with ultraviolet irradiation, and drying for 1h at the temperature of 140 ℃ to obtain the positive electrode plate.
The invention provides a preparation method of an ultraviolet light curing softening and cracking preventing agent, positive electrode slurry and a preparation method thereof, and a preparation method of a positive electrode plate, which have the beneficial effects that:
1. The positive electrode slurry prepared by the method has high solid content, is lower in viscosity and more stable, and can reduce the consumption of a dispersing agent;
2. the positive electrode slurry prepared by the invention is not easy to crack when the pole piece with high thickness is coated;
3. The preparation process flow of the positive electrode slurry is simple;
4. the adhesive force of the positive electrode slurry prepared by the invention to the aluminum foil is high;
5. the anode slurry prepared by the invention has good flexibility, does not need to use a complex coating process, and reduces the production cost.
Drawings
FIG. 1 is an enlarged view showing the degree of cracking of a positive electrode sheet prepared by using an ultraviolet light curing softening and cracking preventing agent prepared in example 1 of the present invention;
FIG. 2 is an enlarged view showing the degree of cracking of a positive electrode sheet prepared by using an ultraviolet light curing softening and cracking preventing agent prepared in example 2 of the present invention;
FIG. 3 is an enlarged view showing the degree of cracking of a positive electrode sheet prepared by using an ultraviolet light curing softening and cracking preventing agent prepared in example 3 of the present invention;
FIG. 4 is an enlarged view showing the degree of cracking of a positive electrode sheet prepared by using an ultraviolet light curing softening and cracking preventing agent prepared in example 4 of the present invention;
FIG. 5 is an enlarged view showing the degree of cracking of a positive electrode sheet prepared by using an ultraviolet light curing softening and cracking preventing agent prepared in example 5 of the present invention;
fig. 6 is an enlarged view of the degree of cracking of the positive electrode sheet in comparative example 1;
fig. 7 is an enlarged view of the degree of cracking of the positive electrode sheet in comparative example 2.
Detailed Description
The preparation method of the ultraviolet light curing softening and cracking preventing agent comprises the following steps:
step one, synthesizing phosphoric triol (p): adding a proper amount of glycidyl ether (b) into a first reaction bottle (four-neck flask) provided with a stirrer, a condenser pipe and a thermometer, stirring and heating to 70 ℃, then slowly adding the phosphoric diester (a) into the first reaction bottle within 1h, continuing stirring, keeping the temperature at 70 ℃, heating to 90-100 ℃ after the phosphoric diester (a) is added, and reacting for about 3h, finally leading the pH value of a reactant to be lower than 10 and the epoxy value to be lower than 0.01, thus obtaining the product phosphoric triol (p). The specific reaction formula is as follows:
，
Wherein the molar ratio of the phosphoric diester (a) to the glycidyl ether (b) is 3:1; r in the phosphoric diester (a) represents any one of n-butyl (n-butyl), methyl, phenyl and tolyl; the phosphoric diester (a) is selected from any one of dibutyl phosphate, dimethyl phosphate, dibenzyl phosphate and diphenyl phosphate; r 1 in the glycidyl ether (b) represents the following structural formula:
。
Since the structural formula of the phosphoric triol (p) is complicated, the phosphoric triol (p) prepared in this step is abbreviated as the following structural formula in order to facilitate the understanding of the following steps:
。
Step two, synthesizing trifunctional phosphate modified polyurethane acrylic ester (f): adding a proper amount of diisocyanate (c) into a second reaction bottle (four-neck flask) provided with a stirrer, a condenser tube and a thermometer, stirring, heating to 40-50 ℃, adding a proper amount of Hydroquinone (HQ) and dibutyltin dilaurate (DBTDL) into the second reaction bottle, slowly adding hydroxyl acrylate (d) into the second reaction bottle, keeping the temperature at 40-50 ℃, obtaining a semi-adduct (e) when the isocyanate content wNCO in the reactant is not changed, quickly adding phosphoric triol (p) and a proper amount of reactive diluent into the second reaction bottle, simultaneously raising the temperature and keeping the temperature at 70 ℃, and reacting until NCO characteristic peaks cannot be detected, thus obtaining the trifunctional phosphate modified polyurethane acrylate (f). The specific reaction formula is as follows:
，
Wherein the molar ratio of dibutyltin dilaurate to diisocyanate (c) is 0.5:100-1:100, the molar ratio of hydroquinone to diisocyanate (c) is 0.1:100-0.2:100, the molar ratio of hydroxyl acrylate (d) to diisocyanate (c) is 0.95:1-1:1, the molar ratio of phosphoric triol (p) to diisocyanate (c) is 0.33:1-0.35:1, and the molar ratio of reactive diluent to diisocyanate (c) is 0.25:1-0.5:1; r 2 in the diisocyanate (c) represents any one of tolyl, hexamethylene, isophorone, m-xylylene and benzhydryl, and the diisocyanate (c) is selected from any one of toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), m-Xylene Diisocyanate (XDI) and diphenylmethane diisocyanate (MDI); r 3 in the hydroxyl acrylate (d) represents any one of ethyl and propyl, and the hydroxyl acrylate (d) is selected from any one of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA), preferably hydroxyethyl acrylate (HEA); the reactive diluent is selected from any one or more of Glycidyl Methacrylate (GMA), isopropyl methacrylate (IBOA), tetrahydrofuran methyl methacrylate (THFFA), styrene (ST), vinyl Acetate (VA), N-vinyl pyrrolidone (NVP), 1, 6-hexanediol diacrylate (HDDA), neopentyl glycol diacrylate (NPGDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), preferably tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA).
Step three, synthesizing an ultraviolet light curing softening and cracking preventing agent: adding a proper photoinitiator into trifunctional phosphate modified polyurethane acrylate (f), stirring uniformly at room temperature to prepare the ultraviolet light curing flexibilizer and cracking-resistant agent,
Wherein the addition amount of the photoinitiator accounts for 2-10% of the total weight of the ultraviolet light curing softening and cracking preventing agent; the photoinitiator is selected from any one or more of benzophenone, P- (2-ethylamino) benzophenone, 2- (P-methoxyphenyl) -4, 5-diphenyl-mic tut-tut dimer, 2-dichloro-4-phenoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, and methyl benzoyl benzoate, preferably benzophenone.
The ultraviolet light curing softening and cracking preventing agent can be used as one of the raw materials of the positive electrode slurry. The positive electrode slurry consists of solid materials and an organic solvent, wherein the weight of the organic solvent accounts for 40wt% of the total weight of the positive electrode slurry; the solid material comprises, based on 100wt% of the total weight, 0.1wt% of an ultraviolet light curing softening and cracking preventing agent, 2wt% of a binder, 2.5wt% of a conductive agent and 95.4wt% of lithium iron phosphate. Wherein the binder is selected from one or more of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and polyacrylic acid, preferably fusolin (2032); the conductive agent is selected from one or more of KS-6, KS-15, SFG-6, SFG-15, acetylene black, super P, super S, 350G, carbon fiber, carbon nanotube and active carbon, preferably KS-6 and Super P; the organic solvent is selected from one or more of N-methyl pyrrolidone, ethyl acetate, methyl propionate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, preferably N-methyl pyrrolidone.
In the preparation process of the positive electrode slurry, the mixing sequence of the organic solvent, the ultraviolet light curing softening and cracking preventing agent, the binder and the conductive agent is not particularly limited, the lithium iron phosphate is added at last, the positive electrode slurry is uniformly dispersed in a stirring mode, an ultrasonic mode and the like, and the stirring is preferably uniform by a high-speed deaerating machine.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h.
In order to make the above objects, features and advantages of the present invention more comprehensible, the following embodiments accompanied with examples are further described. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1, this embodiment shows a preparation method of an ultraviolet light curing softening and cracking preventing agent according to the following steps:
Step one: synthesis of phosphoric triol (p)
Adding a proper amount of glycidyl ether (b) into a first reaction bottle (four-neck flask) provided with a stirrer, a condenser pipe and a thermometer, stirring and heating to 70 ℃, then slowly adding dibutyl phosphate (a) into the first reaction bottle within 1h, keeping stirring, keeping the temperature at 70 ℃, heating to 100 ℃ after the dibutyl phosphate (a) is added, and reacting for about 3h, wherein the pH value of a reactant is lower than 10, and the epoxy value is lower than 0.01, thus obtaining the product phosphoric triol (p). The specific reaction formula is as follows:
，
Wherein R in dibutyl phosphate (a) represents n-butyl (n-butyl); r 1 in the glycidyl ether (b) represents the following structural formula:
，
Since the structural formula of the phosphoric triol (p) is complicated, the phosphoric triol (p) prepared in this step is abbreviated as the following structural formula in order to facilitate the understanding of the following steps:
；
Step two: synthesis of trifunctional phosphate modified polyurethane acrylate (f)
Adding a proper amount of toluene 2, 4-diisocyanate (c) into a second reaction bottle (four-neck flask) provided with a stirrer, a condenser pipe and a thermometer, stirring, heating to 40 ℃, adding a proper amount of hydroquinone and dibutyltin dilaurate into the second reaction bottle, slowly adding hydroxyethyl acrylate (d) into the second reaction bottle, keeping the temperature at 40 ℃, obtaining a semi-additive (e) when wNCO of reactants are not changed, quickly adding phosphoric triol (p) and a proper amount of tripropylene glycol diacrylate and trimethylolpropane triacrylate into the second reaction bottle, and simultaneously raising and keeping the temperature at 70 ℃ until NCO characteristic peaks cannot be detected in the reaction to obtain the trifunctional phosphate modified polyurethane acrylate (f). The specific reaction formula is as follows:
，
Wherein, the mol ratio of hydroquinone to toluene 2, 4-diisocyanate is 0.5:100, the mol ratio of dibutyl tin dilaurate to toluene 2, 4-diisocyanate is 0.2:100, the mol ratio of hydroxyethyl acrylate to toluene 2, 4-diisocyanate is 1:1, the mol ratio of phosphoric triol to toluene 2, 4-diisocyanate is 0.33:1, and the mol ratio of tripropylene glycol diacrylate, trimethylolpropane triacrylate to toluene 2, 4-diisocyanate is 0.15:0.1:1; r 2 in toluene 2, 4-diisocyanate (c) represents tolyl, R 3 in hydroxyethyl acrylate (d) represents ethyl;
Step three: synthesis of ultraviolet light solidified softening and cracking preventing agent
Adding a proper amount of benzophenone into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the benzophenone accounts for 5% of the total amount of the ultraviolet light curing flexibilizer anti-cracking agent.
The ultraviolet light curing softening and cracking preventing agent can be used as one of the raw materials of the positive electrode slurry. The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binol (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.4wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, firstly, an ultraviolet light curing softening and cracking preventing agent, fusline (2032), KS-6, super P and N-methyl pyrrolidone are mixed together, stirred in a deaerator at a rotating speed of 800rpm/min for 20s, and then added with lithium iron phosphate and stirred in the deaerator at a rotating speed of 2000rpm/min for 20min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h to obtain the positive electrode plate.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Example 2, this embodiment shows a preparation method of an ultraviolet light curing softening and cracking preventing agent according to the following steps:
Step one: synthesis of phosphoric triol (p)
A proper amount of glycidyl ether (b) was added to a first reaction flask (four-necked flask) equipped with a stirrer, a condenser and a thermometer, stirred and heated to 70 ℃, and then dimethyl phosphate (a) was slowly added to the first reaction flask over 1 hour, the molar ratio of dimethyl phosphate (a) to glycidyl ether (b) was 3:1, stirring was continued, and the temperature was maintained at 70 ℃. After the dimethyl phosphate (a) is added, the temperature is raised to 95 ℃ for further reaction for about 3 hours, and finally the pH value of the reactant is lower than 10, and the epoxy value is lower than 0.01, thus obtaining the product phosphoric triol (p). The specific reaction formula is as follows:
，
wherein R in the dimethyl phosphate (a) represents methyl; r 1 in the glycidyl ether (b) represents the following structural formula:
，
Since the structural formula of the phosphoric triol (p) is complicated, the phosphoric triol (p) prepared in this step is abbreviated as the following structural formula in order to facilitate the understanding of the following steps:
；
Step two: synthesis of trifunctional phosphate modified polyurethane acrylate (f)
An appropriate amount of isophorone diisocyanate (c) was added to a second reaction flask (four-necked flask) equipped with a stirrer, a condenser and a thermometer, stirred, heated to 45 ℃, an appropriate amount of hydroquinone and dibutyltin dilaurate were added to the second reaction flask, and hydroxyethyl acrylate (d) was slowly added to the second reaction flask and incubated at 45 ℃. When the wNCO of the reactant is not changed any more, a semi-additive (e) is obtained, then the phosphoric triol (p) and a proper amount of tripropylene glycol diacrylate and trimethylolpropane triacrylate are quickly added into a second reaction bottle, the temperature is raised and kept at 70 ℃, and NCO characteristic peaks cannot be detected after the reaction until infrared detection, thus obtaining the trifunctional phosphate modified polyurethane acrylate (f). The specific reaction formula is as follows:
，
Wherein, the mol ratio of hydroquinone to isophorone diisocyanate is 0.75:100, the mol ratio of dibutyl tin dilaurate to isophorone diisocyanate is 0.15:100, the mol ratio of hydroxyethyl acrylate to isophorone diisocyanate is 0.95:1, the mol ratio of phosphoric triol to isophorone diisocyanate is 0.34:1, and the mol ratio of tripropylene glycol diacrylate, trimethylol propane triacrylate to isophorone diisocyanate is 0.2:0.15:1; r 2 in isophorone diisocyanate (c) represents isophorone radical, R 3 in hydroxyethyl acrylate (d) represents ethyl;
Step three: synthesis of ultraviolet light solidified softening and cracking preventing agent
Adding a proper amount of benzophenone into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the benzophenone accounts for 2% of the total amount of the ultraviolet light curing flexibilizer anti-cracking agent.
The ultraviolet light curing softening and cracking preventing agent can be used as one of the raw materials of the positive electrode slurry. The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binol (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.4wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, firstly, an ultraviolet light curing softening and cracking preventing agent, fusline (2032), KS-6, super P and N-methyl pyrrolidone are mixed together, stirred in a deaerator at a rotating speed of 800rpm/min for 20s, and then added with lithium iron phosphate and stirred in the deaerator at a rotating speed of 2000rpm/min for 20min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h to obtain the positive electrode plate.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Example 3, this embodiment shows a preparation method of an ultraviolet light curing softening and cracking preventing agent according to the following steps:
Step one: synthesis of phosphoric triol (p)
Adding a proper amount of glycidyl ether (b) into a first reaction bottle (four-neck flask) provided with a stirrer, a condenser pipe and a thermometer, stirring and heating to 70 ℃, slowly adding dibenzyl phosphate (a) into the first reaction bottle within 1h, keeping stirring, keeping the temperature at 70 ℃, heating to 90 ℃ after the dibenzyl phosphate (a) is added, and reacting for about 3h, wherein the pH value of the reactant is lower than 10, the epoxy value is lower than 0.01, and obtaining the product phosphoric triol (p). The specific reaction formula is as follows:
，
Wherein R in dibenzyl phosphate (a) represents a tolyl group; r 1 in the glycidyl ether (b) represents the following structural formula:
，
Since the structural formula of the phosphoric triol (p) is complicated, the phosphoric triol (p) prepared in this step is abbreviated as the following structural formula in order to facilitate the understanding of the following steps:
；
Step two: synthesis of trifunctional phosphate modified polyurethane acrylate (f)
A proper amount of hexamethylene diisocyanate (c) was added to a second reaction flask (four-necked flask) equipped with a stirrer, a condenser and a thermometer, stirred, heated to 50 ℃, a proper amount of hydroquinone and dibutyltin dilaurate were added to the second reaction flask, and hydroxyethyl acrylate (d) was slowly added to the second reaction flask and kept at 50 ℃. When the wNCO of the reactant is not changed any more, a semi-additive (e) is obtained, then the phosphoric triol (p) and a proper amount of tripropylene glycol diacrylate and trimethylolpropane triacrylate are quickly added into a second reaction bottle, the temperature is raised and kept at 70 ℃, and NCO characteristic peaks cannot be detected after the reaction until infrared detection, thus obtaining the trifunctional phosphate modified polyurethane acrylate (f). The specific reaction formula is as follows:
，
wherein, the mol ratio of hydroquinone to hexamethylene diisocyanate is 1:100, the mol ratio of dibutyl tin dilaurate to hexamethylene diisocyanate is 0.1:100, the mol ratio of hydroxyethyl acrylate to hexamethylene diisocyanate is 0.95:1, the mol ratio of phosphoric triol to hexamethylene diisocyanate is 0.35:1, and the mol ratio of tripropylene glycol diacrylate, trimethylolpropane triacrylate to hexamethylene diisocyanate is 0.1:0.25:1; r 2 in hexamethylene diisocyanate (c) represents hexamethylene and R 3 in hydroxyethyl acrylate (d) represents ethyl;
Step three: synthesis of ultraviolet light solidified softening and cracking preventing agent
Adding a proper amount of benzophenone into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the benzophenone accounts for 7% of the total amount of the ultraviolet light curing flexibilizer anti-cracking agent.
The ultraviolet light curing softening and cracking preventing agent can be used as one of the raw materials of the positive electrode slurry. The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binol (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.4wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, firstly, an ultraviolet light curing softening and cracking preventing agent, fusline (2032), KS-6, super P and N-methyl pyrrolidone are mixed together, stirred in a deaerator at a rotating speed of 800rpm/min for 20s, and then added with lithium iron phosphate and stirred in the deaerator at a rotating speed of 2000rpm/min for 20min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h to obtain the positive electrode plate.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Example 4, this embodiment shows a preparation method of an ultraviolet light curing softening and cracking preventing agent according to the following steps:
Step one: synthesis of phosphoric triol (p)
Adding a proper amount of glycidyl ether (b) into a first reaction bottle (four-neck flask) provided with a stirrer, a condenser pipe and a thermometer, stirring and heating to 70 ℃, then slowly adding diphenyl phosphate (a) into the first reaction bottle within 1h, keeping stirring, keeping the temperature at 70 ℃, heating to 100 ℃ after the diphenyl phosphate (a) is added, and reacting for about 3h, wherein the pH value of the reactant is lower than 10, the epoxy value is lower than 0.01, and obtaining the product phosphoric triol (p). The specific reaction formula is as follows:
，
Wherein R in diphenyl phosphate (a) represents phenyl; r 1 in the glycidyl ether (b) represents the following structural formula:
，
Since the structural formula of the phosphoric triol (p) is complicated, the phosphoric triol (p) prepared in this step is abbreviated as the following structural formula in order to facilitate the understanding of the following steps:
；
Step two: synthesis of trifunctional phosphate modified polyurethane acrylate (f)
A proper amount of m-xylene diisocyanate (c) was added to a second reaction flask (four-necked flask) equipped with a stirrer, a condenser and a thermometer, stirred, heated to 45 ℃, a proper amount of hydroquinone and dibutyltin dilaurate were added to the second reaction flask, and hydroxyethyl acrylate (d) was slowly added to the second reaction flask and kept warm to 45 ℃. When the wNCO of the reactant is not changed any more, a semi-additive (e) is obtained, then the phosphoric triol (p) and a proper amount of tripropylene glycol diacrylate and trimethylolpropane triacrylate are quickly added into a second reaction bottle, the temperature is raised and kept at 70 ℃, and NCO characteristic peaks cannot be detected after the reaction until infrared detection, thus obtaining the trifunctional phosphate modified polyurethane acrylate (f). The specific reaction formula is as follows:
，
Wherein, the mol ratio of hydroquinone to m-xylene diisocyanate is 0.5:100, the mol ratio of dibutyl tin dilaurate to m-xylene diisocyanate is 0.15:100, the mol ratio of hydroxyethyl acrylate to m-xylene diisocyanate is 1:1, the mol ratio of phosphoric triol to m-xylene diisocyanate is 0.35:1, and the mol ratio of tripropylene glycol diacrylate, trimethylolpropane triacrylate to m-xylene diisocyanate is 0.2:0.3:1; r 2 in the meta-xylene diisocyanate (c) represents m-xylylene and R 3 in the hydroxyethyl acrylate (d) represents ethyl;
Step three: synthesis of ultraviolet light solidified softening and cracking preventing agent
Adding a proper amount of benzophenone into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the benzophenone accounts for 10% of the total amount of the ultraviolet light curing flexibilizer anti-cracking agent.
The ultraviolet light curing softening and cracking preventing agent can be used as one of the raw materials of the positive electrode slurry. The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binol (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.4wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, firstly, an ultraviolet light curing softening and cracking preventing agent, fusline (2032), KS-6, super P and N-methyl pyrrolidone are mixed together, stirred in a deaerator at a rotating speed of 800rpm/min for 20s, and then added with lithium iron phosphate and stirred in the deaerator at a rotating speed of 2000rpm/min for 20min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h to obtain the positive electrode plate.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Example 5, this embodiment shows a preparation method of an ultraviolet light curing softening and cracking preventing agent according to the following steps:
Step one: synthesis of phosphoric triol (p)
Adding a proper amount of glycidyl ether (b) into a first reaction bottle (four-neck flask) provided with a stirrer, a condenser pipe and a thermometer, stirring and heating to 70 ℃, then slowly adding dibutyl phosphate (a) into the first reaction bottle within 1h, keeping stirring, keeping the temperature at 70 ℃, heating to 95 ℃ after the dibutyl phosphate (a) is added, and reacting for about 3h, wherein the pH value of a reactant is lower than 10, and the epoxy value is lower than 0.01, thus obtaining the product phosphoric triol (p). The specific reaction formula is as follows:
，
Wherein R in dibutyl phosphate (a) represents n-butyl (n-butyl); r 1 in the glycidyl ether (b) represents the following structural formula:
，
Since the structural formula of the phosphoric triol (p) is complicated, the phosphoric triol (p) prepared in this step is abbreviated as the following structural formula in order to facilitate the understanding of the following steps:
；
Step two: synthesis of trifunctional phosphate modified polyurethane acrylate (f)
A proper amount of diphenylmethane diisocyanate (c) was added to a second reaction flask (four-necked flask) equipped with a stirrer, a condenser and a thermometer, stirred, heated to 50 ℃, a proper amount of hydroquinone and dibutyltin dilaurate were added to the second reaction flask, and hydroxyethyl acrylate (d) was slowly added to the second reaction flask and incubated to 50 ℃. When the wNCO of the reactant is not changed any more, a semi-additive (e) is obtained, then the phosphoric triol (p) and a proper amount of tripropylene glycol diacrylate and trimethylolpropane triacrylate are quickly added into a second reaction bottle, the temperature is raised and kept at 70 ℃, and NCO characteristic peaks cannot be detected after the reaction until infrared detection, thus obtaining the trifunctional phosphate modified polyurethane acrylate (f). The specific reaction formula is as follows:
，
wherein, the mol ratio of hydroquinone to diphenylmethane diisocyanate is 0.75:100, the mol ratio of dibutyltin dilaurate to diphenylmethane diisocyanate is 0.1:100, the mol ratio of hydroxyethyl acrylate to diphenylmethane diisocyanate is 1:1, the mol ratio of phosphoric triol to diphenylmethane diisocyanate is 0.34:1, and the mol ratio of tripropylene glycol diacrylate, trimethylolpropane triacrylate to diphenylmethane diisocyanate is 0.4:0.1:1; r 2 in diphenylmethane diisocyanate (c) represents benzhydryl and R 3 in hydroxyethyl acrylate (d) represents ethyl;
Step three: synthesis of ultraviolet light solidified softening and cracking preventing agent
Adding a proper amount of benzophenone into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the benzophenone accounts for 6% of the total amount of the ultraviolet light curing flexibilizer anti-cracking agent.
The ultraviolet light curing softening and cracking preventing agent can be used as one of the raw materials of the positive electrode slurry. The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binol (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.4wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, firstly, an ultraviolet light curing softening and cracking preventing agent, fusline (2032), KS-6, super P and N-methyl pyrrolidone are mixed together, stirred in a deaerator at a rotating speed of 800rpm/min for 20s, and then added with lithium iron phosphate and stirred in the deaerator at a rotating speed of 2000rpm/min for 20min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h to obtain the positive electrode plate.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Comparative example 1
The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 2wt% of fusolin (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.5wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, the Funo lin (2032), the KS-6, the Super P and the N-methyl pyrrolidone are mixed together, stirred for 20s in a deaerator at a rotating speed of 800rpm/min, and then added with the lithium iron phosphate and stirred for 20min in the deaerator at a rotating speed of 2000rpm/min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: and taking aluminum foil as a base material, uniformly coating the positive electrode slurry on the base material, forming the coated positive electrode slurry into a thickness of 350 mu m, and then placing the base material in an oven with ultraviolet irradiation, and drying at 140 ℃ for 1h to obtain the positive electrode plate.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Comparative example 2
The positive electrode slurry consists of a solid material and N-methyl pyrrolidone, wherein the weight of the N-methyl pyrrolidone accounts for 40wt% of the total weight of the positive electrode slurry; the solid material formula is as follows: 2wt% of fusolin (2032), 1wt% of KS-6, 1.5wt% of Super P and 95.5wt% of lithium iron phosphate.
In the preparation process of the positive electrode slurry, the Funo lin (2032), the KS-6, the Super P and the N-methyl pyrrolidone are mixed together, stirred for 20s in a deaerator at a rotating speed of 800rpm/min, and then added with the lithium iron phosphate and stirred for 20min in the deaerator at a rotating speed of 2000rpm/min, so that the positive electrode slurry is obtained.
The positive electrode slurry can be applied to a positive electrode plate, and the specific application method is as follows: uniformly coating the anode slurry on the surface of an aluminum foil with the thickness of 200 mu m, putting the aluminum foil into an oven with an ultraviolet irradiation device, baking for 20min, uniformly coating the anode slurry on the surface of a pole piece with the thickness of 150 mu m, and putting the pole piece into the oven with the ultraviolet irradiation device, baking for 40min to obtain the anode pole piece.
The pole piece was rolled until the compaction density reached 2.4g/m 3 and tested for pole piece peel force.
Table 1 shows the results of the positive electrode slurry performance test of comparative examples 1 and 2 and examples 1 to 5.
TABLE 1
The viscosity test methods mentioned in table 1 are: the sample (positive electrode slurry) was placed in a constant temperature water bath at 25℃for 1 hour, measured using an NDJ-5S digital rotary viscometer, using rotor No. 4 rotor at 12rpm, and measured at 25 ℃.
Referring to table 1, from the comparison of examples 1 to 5 and comparative examples 1 and 2, it can be seen that: the discharge viscosity of the positive electrode slurries of examples 1-5 is far lower than that of the positive electrode slurries of comparative examples 1 and 2, and the slurry stability of examples 1-5 is better because the dispersibility and stability of the positive electrode slurries are improved after the ultraviolet light curing softening and cracking preventing agent is modified by phosphate; the positive electrode slurries of examples 1 and 5 had the best dispersion properties because the dibutyl phosphate modified uv curable flexibilizing crack-preventing agent improved the dispersion properties of the positive electrode slurries the greatest.
Table 2 is a table of the results of the rolling peel force and the folding endurance test of the positive electrode sheets of comparative examples 1 and 2 and examples 1 to 5.
TABLE 2
The peel force test methods mentioned in table 2 were: the positive electrode sheet rolled to a compaction density of 2.4g/m 3 was cut into 15mm by 200mm sample strips, which were tested using a 180℃horizontal peel strength tester at a speed of 150mm/min and a test temperature of 23 ℃.
The test methods for the folding endurance mentioned in table 2 are: and (3) cutting the positive electrode plate rolled to a compaction density of 2.4g/m 3 into a sample strip with a thickness of 15mm multiplied by 200mm, and respectively doubling the coated surface and the aluminum foil surface once for one time until the sample strip is cracked.
Referring to table 1, from the comparison of examples 1 to 5 and comparative examples 1 and 2, it can be seen that: the roll stripping force and flexibility of the positive electrode plates of examples 1-5 are obviously better than those of the positive electrode plates of comparative examples 1 and 2, because the ultraviolet light curing softening and cracking preventing agent disclosed by the invention absorbs the radiation energy of ultraviolet light and then splits into free radicals under the irradiation of the ultraviolet light, the prepolymer is initiated to undergo polymerization, crosslinking and grafting reactions, and the prepolymer is cured into a netlike high polymer in a short time, so that the slurry and the aluminum foil base material are firmly adhered together, and the adhesive force of the positive electrode slurry and the base material and the flexibility of the positive electrode slurry are also increased by introducing phosphate; the uv curable flex-enhancing crack-preventing agent of example 1 had the best adhesion and flexibility, followed by the uv curable flex-enhancing crack-preventing agent of example 5.
Referring to fig. 1 to 7, as shown in fig. 1 to 7, there is no crack in fig. 1, there is little crack in fig. 2 to 5, and the crack is evident in fig. 6 to 7. Therefore, the ultraviolet light curing flexibility-increasing cracking-preventing agent can obviously improve the cracking degree of the positive electrode plate, and the improvement of the ultraviolet light curing flexibility-increasing cracking-preventing agent on the cracking of the positive electrode plate is related to the stripping force and the flexibility, and the greater the stripping force, the better the flexibility and the smaller the cracking of the positive electrode plate.
In conclusion, the ultraviolet curing softening and cracking preventing agent disclosed by the invention not only can obviously improve the cracking degree of the positive electrode plate slurry, increase the flexibility and the peeling force of the positive electrode plate, but also can further improve the viscosity and the stability of the positive electrode plate slurry, is simple in manufacturing process, can realize the functions of thickening and preventing cracking of the positive electrode plate without complex process conditions such as two-layer coating and the like, and is suitable for industrial production.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (7)
1. A positive electrode paste comprising an ultraviolet light curing flexibilizing and cracking preventing agent, comprising: a solid material and an organic solvent, the weight of the organic solvent accounting for 40wt% of the total weight of the positive electrode slurry, the solid material accounting for 100wt% of the total weight, comprising: 0.1wt% of ultraviolet light curing softening and cracking preventing agent, 2wt% of binder, 2.5wt% of conductive agent and 95.4wt% of lithium iron phosphate, wherein the binder is any one or a combination of more of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and polyacrylic acid; the conductive agent is any one or a combination of a plurality of KS-6, KS-15, SFG-6, SFG-15, acetylene black, super P, super S, 350G, carbon fiber, carbon nano tube and active carbon; the organic solvent is any one or a combination of a plurality of N-methyl pyrrolidone, ethyl acetate, methyl propionate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, wherein the preparation method of the ultraviolet light curing softening and cracking preventing agent comprises the following steps:
Step one, synthesizing phosphoric triol: adding glycidyl ether into a first reaction bottle, stirring and heating to 70 ℃, then slowly adding phosphoric diester into the first reaction bottle within 1h, continuously stirring, keeping the temperature at 70 ℃, heating to 90-100 ℃ after the phosphoric diester is added, and reacting for 3h until the pH value of a reactant is lower than 10 and the epoxy value is lower than 0.01, thus obtaining a product phosphoric triol;
Step two, synthesizing trifunctional phosphate modified polyurethane acrylic ester: adding diisocyanate into a second reaction bottle, stirring and heating to 40-50 ℃, adding hydroquinone and dibutyltin dilaurate into the second reaction bottle, slowly adding hydroxyl acrylate into the second reaction bottle, keeping the temperature at 40-50 ℃, when the isocyanate content in reactants is constant, obtaining a semi-adduct, quickly adding phosphoric triol and reactive diluent into the second reaction bottle, simultaneously raising and keeping the temperature at 70 ℃, reacting until no NCO characteristic peak is detected by infrared, and obtaining the trifunctional phosphate modified polyurethane acrylate, wherein the molar ratio of dibutyltin dilaurate to the diisocyanate is 0.5: 100-1: 100; the molar ratio of hydroquinone to diisocyanate was 0.1:100 to 0.2:100; the molar ratio of the hydroxy acrylate to the diisocyanate was 0.95:1 to 1:1, a step of; the molar ratio of the phosphoric triol to the diisocyanate was 0.33:1 to 0.35:1, a step of; the molar ratio of reactive diluent to diisocyanate was 0.25:1 to 0.5:1, a step of;
Step three, synthesizing an ultraviolet light curing softening and cracking preventing agent: adding a photoinitiator into the trifunctional phosphate modified polyurethane acrylate, and uniformly stirring at room temperature to obtain the ultraviolet light curing flexibilizer anti-cracking agent, wherein the addition amount of the photoinitiator accounts for 2% -10% of the total weight of the ultraviolet light curing flexibilizer anti-cracking agent.
2. The positive electrode slurry containing the uv-curable softening and fracture-preventing agent according to claim 1, wherein the reaction formula of the first step is:
，
Wherein,
(A) Is a phosphodiester;
(b) Is a glycidyl ether;
(p) is a phosphoric triol;
r is any one of n-butyl, methyl, phenyl and tolyl;
the structural formula of R 1 is as follows:
。
3. the positive electrode slurry containing the ultraviolet light curing softening and cracking preventing agent according to claim 1, wherein the positive electrode slurry comprises the following components: in step one, the molar ratio of the phosphodiester to the glycidyl ether is 3:1.
4. The positive electrode slurry containing an ultraviolet light curing softening and cracking preventing agent according to claim 1, wherein the abbreviation structural formula of the phosphoric triol is:
，
The reaction formula of the second step is:
，
Wherein,
(C) Is diisocyanate;
(d) Is hydroxy acrylate;
(e) Is a semi-adduct;
(p) is a phosphoric triol;
(f) Is trifunctional phosphate modified polyurethane acrylic ester;
r 2 is any one of tolyl, hexamethylene, isophorone, m-xylylene and benzhydryl;
r 3 is any one of ethyl and propyl.
5. The positive electrode slurry containing the ultraviolet light curing softening and cracking preventing agent according to claim 1, wherein the positive electrode slurry comprises the following components: the phosphoric diester is any one of dibutyl phosphate, dimethyl phosphate, dibenzyl phosphate and diphenyl phosphate; the diisocyanate is any one of toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate and diphenylmethane diisocyanate; the hydroxyl acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the reactive diluent is any one or a combination of a plurality of glycidyl methacrylate, isopropyl methacrylate, tetrahydrofuran methyl methacrylate, styrene, vinyl acetate, N-vinyl pyrrolidone, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate; the photoinitiator is any one or a combination of a plurality of diphenyl ketone, P- (diethylamino) diphenyl ketone, 2- (P-methoxyphenyl) -4, 5-diphenyl imidazole dimer, 2-dichloro-4-phenoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone and methyl benzoylformate.
6. The method for producing a positive electrode slurry according to any one of claims 1 to 5, characterized in that: mixing an organic solvent, an ultraviolet light curing softening and cracking preventing agent, a binder and a conductive agent, and finally adding lithium iron phosphate and uniformly mixing to obtain the anode slurry.
7. A method for producing a positive electrode sheet comprising the positive electrode slurry according to any one of claims 1 to 5, characterized by: and (3) taking aluminum foil as a base material, coating the positive electrode slurry on the base material, wherein the coating thickness of the positive electrode slurry is 350 mu m, then placing the positive electrode slurry in an oven with ultraviolet irradiation, and drying for 1h at the temperature of 140 ℃ to obtain the positive electrode plate.
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